Fluorine-containing material for optical waveguide

ABSTRACT

There is provided a material which can give a high elasticity and heat resistance to an optical waveguide member by photo-curing while maintaining transparency in a near infrared region and further makes it possible to use a film forming process by a spin coating method and a process for producing a waveguide by photolithograph, to obtain a waveguide having a large area and to produce an optical waveguide having reduced water absorption, and further there can be provided an optical waveguide member and an optical waveguide device. Namely, there are provided a fluorine-containing optical waveguide material comprising a curable fluorine-containing prepolymer (I) which is a non-crystalline polymer having a fluorine content of not less than 25% by weight and has a carbon-carbon double bond in a polymer side chain and/or at an end of a polymer trunk chain, an optical waveguide member which is a cured article of the optical waveguide material and an optical waveguide device comprising the optical waveguide member.

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation-in-part of PCT international application No.PCT/JP02/01771 filed on Feb. 27, 2002 pending.

BACKGROUND OF THE INVENTION

The present invention relates to a fluorine-containing material for anoptical waveguide which is produced by curing a fluorine-containingprepolymer having a carbon-carbon double bond in its molecular chain, amember obtained from a cured article of the fluorine-containing materialfor an optical waveguide and an optical waveguide device produced byusing the cured article on at least one of a core portion and a cladportion of the device.

Various optical parts have been developed aiming at a high grade opticalcommunication system and economization thereof. Particularly anattention is directed to an optical waveguide as a basic technology forrealizing a high density optical interconnection and a waveguide typeoptical device. Generally optical waveguide materials are required tohave characteristics such as easiness in production of a waveguide,controllability of transparency in a region of near infrared wavelength,heat resistance and water resistance.

At present quartz is used most as a material for an optical waveguide.Quartz is high in transparency at a wavelength of from 1,300 to 1,550 nmin a near infrared region and is low in light loss. However there is aproblem that a production process is complicated and a waveguide havinga large area is difficult to produce. Therefore it is difficult toproduce a waveguide type optical device which is excellent in economyand can be used widely for various purposes.

On the other hand, in case of an optical waveguide obtained from a highmolecular weight material, since a process for forming a film with aspin coater can be adopted, the waveguide can be produced by an easyprocess and its area can be made large. However since conventionaltransparent resin materials such as polystyrene, acrylic resin andpolyimide have a large absorption in the above-mentioned near infraredregion (poor transparency), a light loss is large and it is difficult touse for the waveguide practically. A trial has been made to reduce lightloss by replacing hydrogen in those resins with heavy oxygen (D) orfluorine (F). As a result, though optical characteristics can beimproved, it was found that those characteristics were loweredsignificantly due to water absorption with a lapse of time. Namely, anabsorption of light in a near infrared region is increased due to water,thereby increasing a transmission loss.

There has been proposed a non-crystalline fluorine-containing perfluoropolymer having a ring structure as a high molecular weight materialwhich has good transparency in a near infrared region, is relatively lowin light loss and has a low water absorption (JP4-190202A,JP2000-81519A, etc.).

Such a non-crystalline fluorine-containing polymer has no problem withtransparency, but is low in a glass transition temperature and has aproblem with heat resistance. In case of a system where the glasstransition temperature was sufficiently increased by changing thestructure and proportion of its components, the polymer became fragileand there was a problem that cracking occurred in a process of forming awaveguide. Also in case of the non-crystalline fluorine-containingperfluoro polymer, a range of controllable refractive index is narrowand there is a big restriction in designing of a core-clad typewaveguide. For example, when the polymer is used on the core portion ofa waveguide, since there is no proper clad material from the viewpointof refractive index, as mentioned in JP2000-81519A, it is necessary toblend a compound having a high refractive index to the core portion. Incase of such a core material, there is a disadvantage that the blendedhigh refractive index component is re-dispersed due to a factor such asan external environmental, which causes non-uniformity of a refractiveindex inside the core and becomes an influential factor of atransmission loss. As mentioned above, all the problems with thematerial for a waveguide have not been solved and a novel material for awaveguide which can solve those problems is desired.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a fluorine-containingmaterial for an optical waveguide which can realize a high elasticityand heat resistance of the optical waveguide by the use of a specificfluorine-containing prepolymer and photo-curing while maintainingtransparency in a near infrared region (hereinafter referred to as “nearinfrared transparency”).

Also an object of the present invention is to provide a material for awaveguide which makes it possible to use a film forming process by aspin coating method, to use a process for producing a waveguide byphotolithography, to obtain a large area and to reduce water absorptionwhile maintaining a near infrared transparency.

Further an object of the present invention is to provide an opticalwaveguide member and optical waveguide device which are produced usingthe above-mentioned material.

The present inventors have made intensive studies to achieve theabove-mentioned objects and have found a non-crystallinefluorine-containing prepolymer having a carbon-carbon double bond in thepolymer side chain or at an end of the polymer trunk chain and havefound that by the use of the prepolymer, a cured article having highheat resistance can be obtained without lowering near infraredtransparency.

Further the present inventors have found that a cured film obtained froma specific fluorine-containing prepolymer having a carbon-carbon doublebond at an end of its side chain is useful as a material for an opticalwaveguide which has both of near infrared transparency and heatresistance.

Based on those findings, the present inventors have completed thepresent invention.

The first of the present invention relates to a fluorine-containingmaterial for an optical waveguide comprising a fluorine-containingprepolymer (I) which is a non-crystalline polymer having a fluorinecontent of not less than 25% by weight and has an ethyleniccarbon-carbon double bond in the polymer side chain and/or at an end ofthe polymer trunk chain.

Example of the fluorine-containing prepolymer (I) which is used suitablyin the present invention is a fluorine-containing polymer having anumber average molecular weight of from 500 to 1,000,000 and representedby the formula (1):

 MA  (1)

in which the structural unit M is a structural unit derived from afluorine-containing ethylenic monomer and represented by the formula(M):

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; X⁴ and X⁵ are the same or different and each is H, F orCF₃; Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to3; b and c are the same or different and each is 0 or 1,the structural unit A is a structural unit derived from monomercopolymerizable with the fluorine-containing ethylenic monomer providingthe structural unit M,and the structural unit M and the structural unit A are contained inamounts of from 0.1 to 100% by mole and from 0 to 99.9% by mole,respectively.

More preferred fluorine-containing prepolymer (I) is afluorine-containing prepolymer having a maximum absorption coefficientof not more than 1 cm⁻¹ at a wavelength of from 1,290 to 1,320 and/or ata wavelength of from 1,530 to 1,570.

The second of the present invention relates to a fluorine-containingoptical waveguide member obtained from a cured article of thefluorine-containing prepolymer (I) or a cured article obtained byphoto-curing a composition comprising the fluorine-containing prepolymer(I) and in addition, an active energy curing initiator (II) such as aphotoradical generator (II-1) or a photoacid generator (II-2), in whicha maximum absorption coefficient of those cured articles is not morethan 1 cm⁻¹ at a wavelength of from 1,290 to 1,320 and/or at awavelength of from 1,530 to 1,570.

The third of the present invention relates to an optical waveguidedevice in which the fluorine-containing optical waveguide member of thesecond invention is used on a core portion and/or a clad portion of thedevice.

The present invention also relates to a method of producing an opticalwaveguide device which comprises the following steps (A) to (C):

-   (A) a step for forming a clad portion on a substrate,-   (B) a step for forming, on the clad portion, a film of    fluorine-containing waveguide material comprising a curable    fluorine-containing prepolymer (I) which:-   (1) is a non-crystalline polymer having a fluorine content of not    less than 25% by weight and-   (2) has a carbon-carbon double bond in the polymer side chain and/or    at an end of the polymer trunk chain and an active energy curing    initiator (II), and-   (C) a step for forming a core portion comprising a cured article of    the fluorine-containing prepolymer (I) by irradiating the film of    fluorine-containing waveguide material with active energy ray.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagrammatic cross-sectional view of the optical waveguidedevice of the present invention.

FIGS. 2(a)-2(d) represent a flow chart for explaining production stepsof the optical waveguide device of the present invention.

FIG. 3 is a graph showing an absorption loss at each wavelength of aphoto-cured film produced in Example 31.

DETAILED DESCRIPTION

As mentioned supra, the fluorine-containing prepolymer (I) which is usedsuitably in the present invention is a fluorine-containing polymerhaving a number average molecular weight of from 500 to 1,000,000 andrepresented by the formula (1):MA  (1)in which the structural unit M is a structural unit derived from afluorine-containing ethylenic monomer and represented by the formula(M):

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; X⁴ and X⁵ are the same or different and each is H, F orCF₃; Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to3; b and c are the same or different and each is 0 or 1,the structural unit A is a structural unit derived from monomercopolymerizable with the fluorine-containing ethylenic monomer providingthe structural unit M,and the structural unit M and the structural unit A are contained inamounts of from 0.1 to 100% by mole and from 0 to 99.9% by mole,respectively.

Namely, the prepolymer (I) is a homopolymer of the structural unit Mderived from a fluorine-containing ethylenic monomer providing, in apolymer side chain, an ethylenic carbon-carbon double bond curable by areaction or a copolymer containing the structural unit M as an essentialcomponent.

In the Rf of the structural unit M, it is preferable that at least oneof Y¹ is bonded to an end of the Rf.

In the fluorine-containing prepolymer (I) which is used in the presentinvention, the structural unit M is preferably a structural unit M1derived from a fluorine-containing ethylenic monomer and represented bythe formula (M1):

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; X⁴ and X⁵ are the same or different and each is H, F orCF₃; Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to3; c is 0 or 1.

The fluorine-containing prepolymer having the structural unit M1 ispreferred since particularly near infrared transparency is high and incase of not only a homopolymer of the structural unit M1 but also acopolymer containing an increased amount of the structural unit M1, nearinfrared transparency can be made high.

Further example of the preferred structural unit M1 is a structural unitM2 derived from a fluorine-containing ethylenic monomer and representedby the formula (M2):

wherein Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond.

The structural unit M2 is a structural unit of a fluorine-containingallyl ether having an ethylenic carbon-carbon double bond at its end andis preferred since not only near infrared transparency can be made highbut also its polymerizability is good, particularly homopolymerizabilityand copolymerizability with other fluorine-containing ethylenic monomerare good.

Also another example of the preferred structural unit M1 is a structuralunit M3 derived from a fluorine-containing ethylenic monomer andrepresented by the formula (M3):

wherein Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond.

The structural unit M3 is a structural unit of a fluorine-containingvinyl ether having an ethylenic carbon-carbon double bond at its end andis preferred since near infrared transparency can be made high and alsoits copolymerizability with other fluorine-containing ethylenic monomeris good.

In the fluorine-containing prepolymer (I) of the formula (1) which isused in the present invention, Y¹ contained in the structural units M,M1, M2 and M3 is, as mentioned above, a monovalent organic group having2 to 10 carbon atoms and an ethylenic carbon-carbon double bond at itsend.

The carbon-carbon double bond in Y¹ has an ability of causing apolycondensation reaction, etc. and can provide a cured (crosslinked)article. Concretely, for example, a polymerization reaction andcondensation reaction are caused between the molecules of thefluorine-containing prepolymer (I) or between the fluorine-containingprepolymer (I) and a curing (crosslinking) agent to be added as casedemands by contact with a radical or a cation, and thereby a cured(crosslinked) article can be provided.

The first of the preferred Y¹ is:O_(d)C═O_(e)Y²wherein Y² is an alkenyl group or fluorine-containing alkenyl grouphaving 2 to 5 carbon atoms and an ethylenic carbon-carbon double bond atits end; d and e are the same or different and each is 0 or 1.

Example of preferred Y² is:—CX⁶═CX⁷X⁸wherein X⁶ is H, F, CH₃ or CF₃; X⁷ and X⁸ are the same or different andeach is H or F. This group is preferred because of a high curingreactivity by contact with a radical or a cation.

Examples of the preferred Y² are:

and the like.

Also more preferred Y¹ is:—O(C═O)CX⁶═CX⁷X⁸wherein X⁶ is H, F, CH₃ or CF₃; X⁷ and X⁸ are the same or different andeach is H or F. This group is particularly preferred because a curingreactivity by contact with a radical is high and a cured article can beobtained easily by photo-curing.

Examples of the more preferred Y¹ are:

and the like.

Examples of other preferred Y¹ are:

and the like.

Among the Y¹, those which have the structure of —O(C═O)CF═CH₂ ispreferred because near infrared transparency can be made high, a curing(crosslinking) reactivity is particularly high and a cured article canbe obtained efficiently.

The above-mentioned organic group Y¹ having a carbon-carbon double bondin its side chain may be introduced to an end of the polymer trunkchain.

In the fluorine-containing prepolymer (I) which is used in the presentinvention, —Rf— (a group obtained by excluding Y¹ from the —Rf)contained in the structural units M, M1, M2 and M3 is afluorine-containing alkylene group having 1 to 40 carbon atoms or afluorine-containing alkylene group having 2 to 100 carbon atoms andether bond.

This —Rf— group is one in which fluorine atom is bonded to carbon atomcontained therein. The —Rf— group is generally a fluorine-containingalkylene group or fluorine-containing alkylene group having ether bondin which fluorine atom and hydrogen atom or chlorine atom are bonded tocarbon atom. Preferred —Rf— group is one having more fluorine atoms (ahigh fluorine content). More preferred is a perfluoroalkylene group or aperfluoroalkylene group having ether bond. The fluorine content of thefluorine-containing prepolymer (I) is not less than 25% by weight,preferably not less than 40% by weight. Such a fluorine content ispreferred because near infrared transparency of the fluorine-containingprepolymer (I) can be made high and also a high near infraredtransparency can be maintained even if a curing degree (crosslinkingdensity) is increased particularly to increase heat resistance andelasticity of a cured article.

Too large number of carbon atoms of —Rf— is not preferred because thereis a case where solubility in a solvent is lowered and transparency islowered in case of a fluorine-containing alkylene group, and becausehardness and mechanical properties of the polymer itself and the curedarticle are lowered in case of a fluorine-containing alkylene grouphaving ether bond. The number of carbon atoms of the fluorine-containingalkylene group is preferably from 1 to 20, more preferably from 1 to 10.The number of carbon atoms of the fluorine-containing alkylene grouphaving ether bond is preferably from 2 to 30, more preferably from 2 to20.

Examples of preferred —Rf— are:

(X⁹ and X¹² are F or CF₃; X¹⁰ and X¹¹ are H or F; o+p+q is from 1 to 30;r is 0 or 1; s and t are 0 or 1)and the like.

As mentioned above, the structural unit M constituting thefluorine-containing prepolymer (I) of the present invention ispreferably the structural unit M1 and the structural unit M1 ispreferably the structural units M2 and M3. Next, mentioned below arepreferred examples of the structural units M2 and M3.

Examples of the preferred monomers constituting the structural unit M2are:

(n: an integer of from 1 to 30, Y¹ is as defined above)and the like.

More concretely there are:

(Rf¹ and Rf² are perfluoroalkyl groups having 1 to 5 carbon atoms; n isan integer of from 0 to 30; X is H, CH₃, F or CF₃)and the like.

Examples of the preferred monomer constituting the structural unit M3are:

and the like.

More concretely there are:

(Rf¹ and Rf² are perfluoroalkyl groups having 1 to 5 carbon atoms; m isan integer of from 0 to 30; n is an integer of from 1 to 3; X is H, CH₃,F or CF₃)and the like.

Examples of the monomer constituting the structural unit M of thefluorine-containing prepolymer (I) other than the above-mentionedstructural units M2 and M3 are, for instance,

and the like wherein Y¹ and —Rf— are as defined above.

More concretely there are:

and the like, wherein Y¹ is as defined above.

In the fluorine-containing prepolymer (I) of the present invention, thestructural unit A is an optional component. The structural unit A is notlimited particularly as far as it is a monomer copolymerizable with thestructural units M, M1, M2 and M3. The structural unit A may beoptionally selected depending on intended applications and requiredcharacteristics of the fluorine-containing prepolymer and a curedarticle obtained therefrom.

Examples of the structural unit A are, for instance, as follows.

(i) Structural Units Derived from Fluorine-Containing Ethylenic Monomershaving Functional Group

These structural units (i) are preferred from the point that adhesion toa substrate and solubility in a solvent, particularly in ageneral-purpose solvent can be imparted to the fluorine-containingprepolymer (I) and a cured article obtained therefrom while maintaininga high near infrared transparency, and is also preferred from the pointthat functions such as crosslinkability other than those affected by Y¹can be imparted.

Preferred structural unit (i) of the fluorine-containing ethylenicmonomer having functional group is a structural unit represented by theformula (3):

wherein X¹¹, X¹² and X¹³ are the same or different and each is H or F;X¹⁴ is H, F or CF₃; h is 0, 1 or 2; i is 0 or 1; Rf⁴ is afluorine-containing alkylene group having 1 to 40 carbon atoms or afluorine-containing alkylene group having 2 to 100 carbon atoms andether bond; Z¹ is a functional group selected from the group consistingof —OH, —CH₂OH, —COOH, carboxylic acid derivative, —SO₃H, sulfonic acidderivative, epoxy and cyano, and particularly preferred is a structuralunit derived from:CH₂═CFCF₂ORf⁴-Z¹wherein Rf⁴ and Z¹ are as defined above.

More concretely there are preferably structural units derived fromfluorine-containing ethylenic monomers such as:

wherein Z¹ is as defined above.

Also there are preferred structural units derived from monomersrepresented by:CF₂═CFORf⁴-Z¹wherein Rf⁴ and Z¹ are as defined above. More concretely there arestructural units derived from monomers such as:

wherein Z¹ is as defined above.

Examples of the other fluorine-containing ethylenic monomer havingfunctional group are:CF₂═CFCF₂—O—Rf-Z¹, CF₂═CF—Rf-Z¹,CH₂═CH—Rf-Z¹, CH₂═CHO—Rf-Z¹and the like, wherein —Rf— is the same as the above-mentioned —Rf— andZ¹ is as defined above. More concretely there are

and the like, wherein Z¹ is as defined above.

When using the monomer having —OH group, —COOH group or —SO₃H group, itis preferable that an amount thereof is in a range where near infraredtransparency is not lowered.

(ii) Structural Units Derived from Fluorine-Containing EthylenicMonomers not having Functional Group

These structural units (ii) are preferred from the point that a highernear infrared transparency of the fluorine-containing prepolymer (I) anda cured article obtained therefrom can be maintained. Further thesestructural units are preferred from the point that by selecting themonomer, mechanical properties and glass transition temperature of thepolymer can be adjusted, particularly the glass transition temperaturecan be increased by copolymerization with the structural unit M.

Examples of the preferred structural units (ii) of thefluorine-containing ethylenic monomer are those represented by theformula (4):

wherein X¹⁵, X¹⁶ and X¹⁸ are the same or different and each is H or F;X¹⁷ is H, F or CF₃; h1, i1 and j are 0 or 1; Z² is H, F or Cl; Rf⁵ is afluorine-containing alkylene group having 1 to 20 carbon atoms or afluorine-containing alkylene group having 2 to 100 carbon atoms andether bond.

Examples thereof are preferably structural units derived from monomerssuch as:

CH₂═CFCF₂_(n)Z² (Z² is as defined in the formula (4), n is from 1 to10) andCH₂═CHOCH₂CF₂_(n)Z² (Z² is as defined in the formula (4), n is from 1to 10)(iii) Fluorine-Containing Aliphatic Ring Structural Units

Introduction of these structural units (iii) is preferred sincetransparency can be increased, a near infrared transparency can beincreased more and further since the fluorine-containing prepolymer (I)having a high glass transition temperature can be obtained and a higherhardness of the cured article can be expected.

Examples of the preferred fluorine-containing aliphatic ring structuralunit (iii) are those represented by the formula (5):

wherein X¹⁹, X²⁰, X²³, X²⁴, X²⁵ and X²⁶ are the same or different andeach is H or F; X²¹ and X²² are the same or different and each is H, F,Cl or CF₃; Rf⁶ is a fluorine-containing alkylene group having 1 to 10carbon atoms or a fluorine-containing alkylene group having 2 to 10carbon atoms and ether bond; n2 is 0 or an integer of from 1 to 3; n1,n3, n4 and n5 are the same or different and each is 0 or 1.

For example, there are structural units represented by:

wherein Rf⁶, X²¹ and X²² are as defined above.

Concretely there are:

and the like wherein X¹⁹, X²⁰, X²³ and X²⁴ are as defined above.

Examples of the other fluorine-containing aliphatic ring structural unitare, for instance,

and the like.(iv) Structural Units Derived from Ethylenic Monomers not havingFluorine

The structural units (iv) derived from ethylenic monomers not havingfluorine may be introduced to the polymer in a range where theintroduction does not have an adverse effect on near infraredtransparency.

The introduction of those structural units (iv) is preferred sincesolubility in a general-purpose solvent is enhanced and compatibilitywith additives, for example, a photocatalyst and a curing agent to beadded as case demands can be improved.

Examples of the non-fluorine-containing ethylenic monomer are asfollows.

α-Olefins:

Ethylene, propylene, butene, vinyl chloride, vinylidene chloride and thelike.

Vinyl ether or vinyl ester monomers:

CH₂═CHOR, CH₂═CHOCOR(R: hydrocarbon group having 1 to 20 carbon atoms)and the like.

Allyl monomers:

CH₂═CHCH₂Cl, CH₂═CHCH₂OH, CH₂═CHCH₂COOH, CH₂═CHCH₂Br and the like.Allyl ether monomers:

and the like.Acrylic or methacrylic monomers:

Acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acidesters, maleic anhydride, maleic acid, maleic acid esters and the like.Monomers obtained by replacing hydrogen atoms of the above-mentionednon-fluorine-containing monomers with heavy hydrogen atoms are morepreferred from the viewpoint of transparency.

(v) Structural Units Derived from Alicyclic Monomers

A structural unit (v) of an alicyclic monomer may be introduced as acomponent copolymerizable with the structural unit M, more preferably asthe third component in addition to the structural unit M and thestructural unit of the above-mentioned fluorine-containing ethylenicmonomer or non-fluorine-containing ethylenic monomer (theabove-mentioned (iii) or (iv)), thereby making a glass transitiontemperature and hardness high.

Examples of the alicyclic monomer (v) are norbornene derivativesrepresented by:

wherein m is 0 or an integer of from 1 to 3; A, B, C and D are the sameor different and each is H, F, Cl, COOH, CH₂OH, a perfluoroalkyl grouphaving 1 to 5 carbon atoms or the like, alicyclic monomers such as:

and derivatives thereof in which a substituent is introduced.

In the fluorine-containing prepolymer (I) of the present invention,various combinations and proportions of the structural units M (M1, M2or M3) and A can be selected from the above-mentioned examples dependingon intended applications, physical properties (particularly glasstransition temperature, hardness, etc.), functions (transparency andnear infrared transparency) and the like as far as the combination ofthe structural units M and A makes the polymer non-crystalline and thefluorine content becomes not less than 25% by weight.

The fluorine-containing prepolymer (I) contains the structural unit M(M1, M2 or M3) as an essential component and is characterized in thatthe structural unit M itself has functions of maintaining a high nearinfrared transparency and imparting transparency and functions of beingcapable of imparting hardness, heat resistance, abrasion resistance,scratch resistance and solvent resistance to a cured article by curing.Also the fluorine-containing prepolymer has a characteristic that arefractive index can be controlled by selecting the content of thestructural unit M. Therefore even if the fluorine-containing prepolymer(I) contains a larger amount of the structural unit M or in the extremecase, even if the prepolymer consists of the structural unit M (100% bymole), a high near infrared transparency can be maintained. Further acured article having a high curing (crosslinking) density can beobtained and a coating film having a high hardness and excellentabrasion resistance, scratch resistance and heat resistance can beobtained.

Also in the case of the copolymer of the fluorine-containing prepolymer(I) comprising the structural unit M and the structural unit A, when thestructural unit A is selected from the above-mentioned examples, therecan be obtained the prepolymer providing a cured article having a higherhardness, a high glass transition temperature and a high near infraredtransparency.

In the copolymer of the fluorine-containing prepolymer (I) comprisingthe structural unit M and the structural unit A, the proportion of thestructural unit M may be not less than 0.1% by mole based on the wholestructural units constituting the fluorine-containing prepolymer (I).The proportion is not less than 2.0% by mole, preferably not less than5% by mole, more preferably not less than 10% by mole in order to obtainthe cured article having a high hardness, excellent abrasion resistanceand scratch resistance and good chemical resistance and solventresistance by curing (crosslinking).

Particularly for the optical waveguide material applications whichrequire formation of a cured coating film having excellent heatresistance and transparency and small moisture absorption, it ispreferable that the structural unit M is contained in an amount of notless than 10% by mole, preferably not less than 20% by mole, morepreferably not less than 50% by mole. An upper limit thereof is lowerthan 100% by mole.

The curable fluorine-containing prepolymer (I) of the present inventionhas preferable characteristics particularly for the optical waveguidematerial applications since near infrared transparency is not loweredeven if the proportion of the structural unit M is increased (or even ifthe number of cure sites is increased).

In case where a high transparency is required in a region of fromvisible light to near infrared ray in optical communicationapplications, it is important that the curable fluorine-containingprepolymer (I) has a combination and proportion of the structural unitsM and A which make the prepolymer non-crystalline. Being non-crystallinemeans that in DSC analysis, when measurement is carried out at a heatingrate of 10° C./min (ASTM D3418-99), an absorption peak derived frommelting is not substantially observed or heat of melting is 1 J/g orlower at the 2nd run.

It is preferable that the fluorine content of the curablefluorine-containing prepolymer (I) is not less than 25% by weight.

If the fluorine content is low, transparency in a near infrared regionis lowered. Also if the fluorine content is low, moisture absorption isincreased and therefore the prepolymer cannot be used substantially asan optical material for optical communication, etc. For the lightamplification material and light emission material applications, mostpreferable fluorine content is not less than 40% by weight. An upperlimit of the fluorine content varies depending on the composition of thefluorine-containing prepolymer (I) and is about 75% by weight which is afluorine content when all hydrogen atoms are replaced with fluorineatoms.

As a method of measuring a fluorine content, generally there is used amethod of calculating the fluorine content by analyzing components of apolymer from measurements with ¹⁹F-NMR and ¹H-NMR. When it is difficultto analyze a polymer structure by the above methods, there is used amethod of elementary analysis of fluorine in which 2 mg of a sample anda combustion improver (10 mg of sodium peroxide) are wrapped with afilter paper (filter paper No.7 available from Toyo Roshi), are put in aplatinum basket and then are burned in a 500 ml flask filled with 25 mlof pure water. Immediately after the burning, the flask is shaken toabsorb fluorine ion in pure water and then fluorine ion absorbed in purewater is analyzed with a fluorine ion electrode (fluorine ion metermodel 901 available from Orion Research).

The molecular weight of the fluorine-containing prepolymer (I) can beselected, for example, in a range of from 500 to 1,000,000 in numberaverage molecular weight, and is preferably from 1,000 to 500,000,particularly preferably from 2,000 to 200,000.

If the molecular weight is too low, mechanical properties are apt to beinsufficient even after the curing, and particularly a cured article anda cured coating film are apt to be fragile and insufficient in strength.If the molecular weight is too high, solubility in a solvent is lowered,particularly film forming property and leveling property are apt to belowered at forming a thin film and storage stability of thefluorine-containing prepolymer is apt to be unstable. For opticalwaveguide applications, most preferable molecular weight is selected ina range of from 5,000 to 100,000 in number average molecular weight.

It is preferable that the fluorine-containing prepolymer (I) itself(before curing) has a maximum absorption coefficient of not more than 1cm⁻¹, more preferably not more than 0.5 cm⁻¹, particularly preferablynot more than 0.1 cm⁻¹ in the wavelength ranges of from 1,290 to 1,320nm and 1,530 to 1,570 nm and further has a refractive index in nd offrom 1.3 to 1.7. Adjustments thereof can be made by determining variouskinds and contents of the structural unit M and kinds of the structuralunit A to be used as case demands and make it possible to selectivelyuse the prepolymer on a core portion or a clad portion of an opticalwaveguide device explained infra.

Further it is preferable that the fluorine-containing prepolymer issoluble in general-purpose solvents, for example, in at least one ofketone solvents, acetic acid ester solvents, alcohol solvents andaromatic solvents or in solvent mixtures containing at least one of theabove-mentioned general-purpose solvents.

When the prepolymer is soluble in general-purpose solvents, it ispreferable because film forming property and homogeneity are excellentparticularly in case of forming a thin coating film of about 3 μm in aprocess for forming an optical waveguide. The prepolymer is alsoadvantageous from the viewpoint of productivity in forming an opticalwaveguide.

Being soluble in a solvent according to the present invention means thatthe fluorine-containing prepolymer is soluble in a solvent in an amountof 10 mg/g, preferably 20 mg/g, more preferably 50 mg/g.

In order to obtain the fluorine-containing prepolymer (I) of the presentinvention, generally any of

-   (i) a method of previously synthesizing a monomer having Y¹ and then    polymerizing the monomer,-   (ii) a method of once synthesizing a polymer having another    functional group and then converting the functional group by high    molecular reaction, thus introducing the functional group Y¹ into    the polymer,    or the like method can be employed.

In the method (i), in order to obtain the fluorine-containing prepolymer(I) having a carbon-carbon double bond in its side chain withoutreacting (curing) the carbon-carbon double bond at an end of its sidechain, it is necessary to change reactivity of two kinds of double bonds(a double bond becoming a trunk chain and a double bond becoming a sidechain) in a (co)polymerizable monomer and thereby make only one of thedouble bonds participate in the polymerization. In such a method, it isdifficult to select the polymerization conditions for obtaining thefluorine-containing prepolymer having a double bond in its side chain,and also it is difficult to obtain a high curing reactivity of thedouble bond in the side chain of the obtained fluorine-containingprepolymer. Therefore the method (ii) is preferred.

The method (ii) is a preferable method since it is easy to obtain thefluorine-containing prepolymer of the present invention without curingreaction and also since a carbon-carbon double bond having a high curingreactivity can be introduced to its side chain and/or an end of itstrunk chain.

Among the methods (ii), as mentioned infra, there is preferablyemployed, for example, a method of synthesizing a fluorine-containingpolymer comprising the structural unit N of a fluorine-containingmonomer having hydroxyl or an organic group Y³ having hydroxyl and ascase demands, the structural unit B of a monomer copolymerizable with N,and then reacting the polymer with an unsaturated carboxylic acid or itsderivative to introduce a carbon-carbon double bond to a side chainand/or an end of a trunk chain of the polymer.

The details of the method are explained below.

The fluorine-containing prepolymer (I) is prepared by esterification ofa fluorine-containing polymer (III) having hydroxyl with an unsaturatedcarboxylic acid or its derivative in which the fluorine-containingpolymer is a polymer represented by the formula (2):NB  (2)in which the structural unit N is a structural unit having hydroxylwhich is derived from a fluorine-containing ethylenic monomer andrepresented by the formula (N):

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; X⁴ and X⁵ are the same or different and each is H, F orCF₃; Rf¹ is an organic group in which 1 to 3 of Y³ (Y³ is hydroxyl or amonovalent organic group having hydroxyl and 1 to 10 carbon atoms) arebonded to a fluorine-containing alkyl group having 1 to 40 carbon atomsor a fluorine-containing alkyl group having 2 to 100 carbon atoms andether bond; a is 0 or an integer of from 1 to 3; b and c are the same ordifferent and each is 0 or 1,the structural unit B is a structural unit derived from monomercopolymerizable with the fluorine-containing ethylenic monomer havinghydroxyl which provides the structural unit N,and the structural unit N and the structural unit B are contained inamounts of from 0.1 to 100% by mole and from 0 to 99.9% by mole,respectively.

In the above-mentioned process for preparing the fluorine-containingprepolymer (I), examples of the preferable structural unit N of thefluorine-containing polymer (III) having hydroxyl which is a precursorrepresented by the formula (2) are structures which correspond to theabove-exemplified respective structural units M of thefluorine-containing prepolymer (I) and have the Y³ having OH groupinstead of the Y¹ having a carbon-carbon double bond. Those structuralunits can be used preferably. As the structural unit B, there can bepreferably used the same structural units as the above-mentionedstructural unit A.

The unsaturated carboxylic acid or its derivative which is reacted withthe fluorine-containing polymer (III) having hydroxyl may be any ofcarboxylic acids or derivatives thereof having a carbon-carbon doublebond at an end thereof. Particularly preferred are α,β-unsaturatedcarboxylic acids or derivatives thereof.

Examples thereof are, for instance, carboxylic acids represented by:

wherein R is H, CH₃, F, CF₃ or Cl, or anhydrides thereof, acid halidesrepresented by:

wherein R is as defined above, X is Cl or F, and in addition, maleicacid, maleic anhydride, maleic acid monoalkylester and the like.

Among them, unsaturated carboxylic acid halides are preferred since thereaction can be carried out at room temperature and gelling of aprepared polymer can be prevented.

Particularly preferred are:

The method of reacting α,β-unsaturated carboxylic acid halide with thefluorine-containing polymer (III) having hydroxyl is not limitedparticularly and may be usually carried out by dissolving thefluorine-containing polymer (III) having hydroxyl in a solvent andmixing the α,β-unsaturated carboxylic acid halide thereto at atemperature of from about −20° C. to about 40° C. with stirring forreaction.

In the reaction, HCl and HF are produced through the reaction, and forcapturing them, it is desirable to add a proper base. Examples of thebase are tertiary amines such as pyridine, N,N-dimethylaniline,tetramethylurea and triethylamine, magnesium metal and the like. Also aninhibitor may be present to prevent a polymerization reaction of thestarting α,β-unsaturated carboxylic acid and the carbon-carbon doublebond in the obtained curable fluorine-containing prepolymer during thereaction.

Examples of the inhibitor are hydroquinone, t-butyl hydroquinone,hydroquinone monomethylether and the like.

The fluorine-containing polymer (III) having hydroxyl before thereaction with the unsaturated carboxylic acid or its derivative can beobtained by (co)polymerizing, through known method, the ethylenicmonomer N having hydroxyl and the monomer B to be used as acopolymerizable component, which correspond to the respective structuralunits. For the polymerization, radical polymerization method, anionpolymerization method, cation polymerization method and the like can beemployed. Among them, the radical polymerization method is preferablyused from the viewpoint that each monomer exemplified to obtain thefluorine-containing polymer (III) having hydroxyl has good radicalpolymerizability, control of composition and molecular weight of theobtained polymer is easy and production in an industrial scale is easy.

In order to initiate the radical polymerization, means for initiation isnot limited particularly as far as the polymerization proceedsradically. The polymerization is initiated, for example, with an organicor inorganic radical polymerization initiator, heat, light, ionizingradiation or the like. The polymerization can be carried out by solutionpolymerization, bulk polymerization, suspension polymerization, emulsionpolymerization or the like. The molecular weight is controlled by thecontents of the monomers to be used for the polymerization, the contentof the polymerization initiator, the content of a chain transfer agent,temperature, etc. The components of the copolymer can be controlled bythe starting monomer components.

The optical waveguide material of the present invention can be obtainedby using the fluorine-containing prepolymer (I) solely and may be in theform of a photo-curable composition by further adding an active energycuring initiator (II) such as a photoradical generator (II-1) or aphotoacid generator (II-2).

The fluorine-containing prepolymer (I) for the material of the presentinvention is the above-mentioned non-crystalline fluorine-containingprepolymer having a carbon-carbon double bond in its side chain and/orat an end of its trunk chain and having a fluorine content of not lessthan 25% by weight. Preferable examples thereof are the same as thosementioned supra.

The active energy curing initiator (II) generates a radical or a cation(acid) only by irradiation of an active energy ray, for example, anelectromagnetic wave having a wavelength of not more than 350 nm such asultraviolet light, electron beam, X-ray or γ-ray and functions as acatalyst for initiating curing (crosslinking reaction) of acarbon-carbon double bond of the fluorine-containing prepolymer. Usuallyan initiator which generates a radical or a cation (acid) by irradiationof ultraviolet light is used and particularly one which generates aradical is used.

According to the photo-curable fluorine-containing resin compositionwhich is the optical waveguide material of the present invention, thecuring reaction can be initiated easily with the above-mentioned activeenergy rays, heating at high temperature is not necessary and the curingreaction can be carried out at relatively low temperature. Therefore thefluorine-containing resin composition is preferred since it can beapplied on a substrate, for example, a transparent resin substrate whichhas a low heat resistance and is apt to be deformed, decomposed orcolored due to heat.

In the material of the present invention, the active energy curinginitiator (II) is optionally selected depending on kind(radical-reactive or cation(acid)-reactive) of the carbon-carbon doublebond in the fluorine-containing prepolymer (I), kind (wavelength range,etc.) of the active energy ray, intensity of irradiation, etc.

Generally examples of the initiator (photoradical generator) whichfunctions to cure the fluorine-containing polymer (I) having aradical-reactive carbon-carbon double bond with active energy ray in anultraviolet region are, for instance, those mentioned below.

Acetophenone Initiators

Acetophenone, chloroacetophenone, diethoxyacetophenone,hydroxyacetophenone, α-aminoacetophenone and the like.

Benzoin Initiators

Benzoin, benzoinmethylether, benzoinethylether, benzoinisopropylether,benzoinisobutylether, benzyldimethylketal and the like.

Benzophenone Initiators

Benzophenone, benzoyl benzoate, methyl-o-benzoylbenzoate,4-phenylbenzophenone, hydroxybenzophenone, hydroxypropylbenzophenone,acrylated benzophenone, Michler's ketone and the like.

Thioxanthone Initiators

Thioxanthone, chlorothioxanthone, methylthioxanthone,diethylthioxanthone, dimethylthioxanthone and the like.

Other Initiators

Benzyl, α-acyloxime ester, acylphosphine oxide, glyoxyester,3-ketocoumaran, 2-ethylanthraquinone, camphorquinone, anthraquinone andthe like.

Also as case demands, an auxiliary for photo-initiation such as amines,sulfones or sulfines may be added.

Also examples of the initiator (photoacid generator) which cures thefluorine-containing prepolymer (I) having a cation(or acid)-reactivecarbon-carbon double bond are those mentioned below.

Onium Salts

Iodonium salt, sulfonium salt, phosphonium salt, diazonium salt,ammonium salt, pyridinium salt and the like.

Sulfone Compounds

β-ketoester, β-sulfonylsulfone, α-diazo compounds thereof and the like.

Sulfonic Acid Esters

Alkylsulfonic acid ester, haloalkylsulfonic acid ester, arylsulfonicacid ester, iminosulfonate and the like.

Others

Sulfonimide compounds, diazomethane compounds and the like.

Examples of the radical-reactive carbon-carbon double bond are, forinstance, those represented by the above-mentioned formula:—O(C═O)CX⁶═CX⁷X⁸and examples of the cation-reactive carbon-carbon double bond are, forinstance, those represented by the above-mentioned formulae:—OCH═CH₂, —C(C═O)OCH═CH₂and the like among those exemplified supra as the preferable Y¹.

In the optical waveguide material of the present invention, the curablefluorine-containing resin composition comprises the fluorine-containingprepolymer (I) and the active energy curing initiator. Further a solventmentioned infra may be added to form a coating solution of thefluorine-containing resin composition and if necessary, a curing agentmay be added to the coating solution.

Preferred curing agents are those which have at least one carbon-carbonunsaturated bond and can be polymerized with a radical or an acid.Examples thereof are radically polymerizable monomers such as acrylicmonomers and cationically polymerizable monomers such as vinyl ethermonomers. Those monomers may be monofunctional monomers having onecarbon-carbon double bond or polyfunctional monomers having two or morecarbon-carbon double bonds.

Those so-called curing agents having a carbon-carbon unsaturated bondreact by a radical or cation generated by a reaction of the activeenergy curing initiator in the material of the present invention with anactive energy ray such as light and can be crosslinked with thecarbon-carbon double bond of the fluorine-containing prepolymer (I) inthe material of the present invention by copolymerization.

Examples of the monofunctional acrylic monomer are acrylic acid, acrylicacid esters, methacrylic acid, methacrylic acid esters, α-fluoroacrylicacid, α-fluoroacrylic acid esters, maleic acid, maleic anhydride, maleicacid esters and (meth)acrylic acid esters having epoxy, hydroxyl,carboxyl or the like.

Among them, particularly preferred are acrylate monomers havingfluoroalkyl group in order to maintain a high near infrared transparencyof a cured article. For example, preferred are compounds represented bythe formula:

wherein X is H, CH₃ or F; Rf¹⁰ is a fluorine-containing alkyl grouphaving 2 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond.

Examples thereof are:

and the like.

As the polyfunctional acrylic monomer, there are generally knowncompounds obtained by replacing hydroxyl groups of polyhydric alcoholssuch as diol, triol and tetraol with acrylate groups, methacrylategroups or α-fluoroacrylate groups.

Examples thereof are compounds obtained by replacing two or morehydroxyl groups of polyhydric alcohols such as 1,3-butanediol,1,4-butanediol, 1,6-hexanediol, diethylene glycol, tripropylene glycol,neopentyl glycol, trimethylol propane, pentaerythritol anddipentaerythritol with any of acrylate groups, methacrylate groups orα-fluoroacrylate groups.

Also there can be used polyfunctional acrylic monomers obtained byreplacing two or more hydroxyl groups of polyhydric alcohols having afluorine-containing alkyl group or a fluorine-containing alkylene groupwith acrylate groups, methacrylate groups or α-fluoroacrylate groups.Those monomers are preferred particularly from the point that a highnear infrared transparency of a cured article can be maintained.

Preferable examples thereof are compounds having a structure obtained byreplacing two or more hydroxyl groups of fluorine-containing polyhydricalcohols represented by the formulae:

(Rf¹¹ is a fluorine-containing alkyl group having 1 to 40 carbon atoms;R is H or an alkyl group having 1 to 3 carbon atoms)

(Rf¹² is a fluorine-containing alkylene group having 1 to 40 carbonatoms; R is H or an alkyl group having 1 to 3 carbon atoms),with acrylate groups, methacrylate groups or α-fluoroacrylate groups.

When those exemplified monofunctional and polyfunctional acrylicmonomers are used as the curing agent for the material of the presentinvention, particularly preferred are α-fluoroacrylate compounds fromthe viewpoint of good curing reactivity.

In the optical waveguide material of the present invention, an addingamount of the active energy curing initiator (II) is optionally selecteddepending on the content of the carbon-carbon double bonds in thefluorine-containing prepolymer (I), an amount of the curing agent andfurther kinds of the initiator and active energy ray and an amount ofirradiation energy (intensity and time) and also depending on whether ornot the above-mentioned curing agent is used. When the curing agent isnot used, the amount of the initiator is from 0.01 to 30 parts byweight, preferably from 0.05 to 20 parts by weight, most preferably from0.1 to 10 parts by weight based on 100 parts by weight of thefluorine-containing prepolymer (I).

Concretely the amount of the initiator is from 0.05 to 50% by mole,preferably from 0.1 to 20% by mole, most preferably from 0.5 to 10% bymole based on the content (the number of moles) of the carbon-carbondouble bonds contained in the fluorine-containing prepolymer (I).

When the curing agent is used, the amount of the initiator is from 0.05to 50% by mole, preferably from 0.1 to 20% by mole, most preferably from0.5 to 10% by mole based on the total number of moles of the content(number of moles) of the carbon-carbon double bonds contained in thefluorine-containing prepolymer (I) and the number of moles of thecarbon-carbon unsaturated bonds of the curing agent.

To the material of the present invention may be added various additivesas case demands in addition to the above-mentioned compounds in therange where near infrared transparency is not lowered.

Examples of the additives are, for instance, a leveling agent, viscositycontrol agent, light-stabilizer, moisture absorbing agent, pigment, dye,reinforcing agent and the like.

The optical waveguide material of the present invention is, as explainedinfra, dissolved or dispersed in a solvent and is used for production ofvarious members for an optical waveguide.

The solvent to be used for making the solution is not limitedparticularly as far as the fluorine-containing prepolymer (I), activeenergy curing initiator (II) and additives to be added as case demandssuch as a curing agent, leveling agent and light stabilizer areuniformly dissolved or dispersed in it. Particularly preferred is asolvent dissolving the fluorine-containing prepolymer (I) uniformly.

Examples of the solvent are, for instance, cellosolve solvents such asmethyl cellosolve, ethyl cellosolve, methyl cellosolve acetate and ethylcellosolve acetate; ester solvents such as diethyl oxalate, ethylpyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, butyl acetate,amyl acetate, ethyl butyrate, butyl butyrate, methyl lactate, ethyllactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl2-hydroxyisobutyrate and ethyl 2-hydroxyisobutyrate; propylene glycolsolvents such as propylene glycol monomethyl ether, propylene glycolmonoethyl ether, propylene glycol monobutyl ether, propylene glycolmonomethyl ether acetate, propylene glycol monoethyl ether acetate,propylene glycol monobutyl ether acetate and dipropylene glycol dimethylether; ketone solvents such as 2-hexanone, cyclohexanone, methyl aminoketone and 2-heptanone; alcohol solvents such as methanol, ethanol,propanol, isopropanol and butanol; aromatic hydrocarbons such as tolueneand xylene; a solvent mixture of two or more thereof and the like.

Also in order to enhance solubility of the fluorine-containingprepolymer (I), a fluorine-containing solvent may be used as casedemands.

Examples of the fluorine-containing solvent are, for instance, CH₃CCl₂F(HCFC-141b), a mixture of CF₃CF₂CHCl₂ and CClF₂CF₂CHClF (HCFC-225),perfluorohexane, perfluoro(2-butyltetrahydrofuran),methoxy-nonafluorobutane, 1,3-bistrifluoromethylbenzene, and inaddition, fluorine-containing alcohols such as:H(CF₂CF₂_(n)CH₂OH (n: an integer of from 1 to 3)F(CF₂_(n)CH₂OH (n: an integer of from 1 to 5) andCF₃CH(CF₃)OH,benzotrifluoride, perfluorobenzene, perfluoro(tributylamine),ClCF₂CFClCF₂CFCl₂ and the like.

Those fluorine-containing solvents may be used solely, in a mixturethereof or in a mixture of one or more of the fluorine-containingsolvents and non-fluorine-containing solvents.

Among them, ketone solvents, acetic acid ester solvents, alcoholsolvents and aromatic solvents are preferred from the viewpoint ofcoatability and productivity of a coating film.

The second of the present invention relates to the fluorine-containingoptical waveguide member which is a cured article obtained byphoto-curing the composition consisting of the fluorine-containingprepolymer (I) or comprising the fluorine-containing prepolymer (I) andthe active energy curing initiator (II).

The cured article is one having a maximum absorption coefficient of notmore than 1 cm⁻¹ in wavelength ranges of from 1,290 to 1,320 nm and from1,530 to 1570 nm.

The optical waveguide member of the second invention is a memberconstituting the optical waveguide device and is formed on a substrate.The optical waveguide device is produced by connecting opticalfunctional devices with an optical waveguide and the optical waveguidecomprises a core portion and a clad portion. On the other hand, theoptical functional device is a device undergoing functions ofamplification, conversion of a wavelength, opticalmultiplex/demultiplex, selection of a wavelength, etc. There are variousforms of functional devices and there are wavegiude type functionaldevices for optical multiplex/demultiplex and optical amplification. Inthat case, the functional devices also comprise a core portion and aclad portion. The member of the present invention can be used on any ofthe core portion and clad portion. The member of the present inventionmay be used only on the core portion or the clad portion. Also it ispossible to add various functional compounds, for example, a non-linearoptical material, a functional organic pigment generating fluorescence,a photo-refractive material and the like to the member of the presentinvention and to use the member as a core material for a waveguide typefunctional device. Further it is preferable that the both of the coreportion and the clad portion are cured articles obtained by curing thefluorine-containing prepolymer.

Namely, the third of the present invention relates to the opticalwaveguide device containing the member of the second invention.

When the optical waveguide device comprises a core portion and a cladportion, a refractive index of the core portion must be higher than thatof the clad portion. A difference in the refractive index between thecore portion and the clad portion is preferably not less than 0.003,more preferably not less than 0.01. Since the refractive index of thematerial and member of the present invention can be controlled in a widerange, the aimed materials can be selected among wide range.

In the optical waveguide device, a width of the core portion ispreferably from 1 to 200 μm, more preferably from 5 to 50 μm. Also apreferred height of the core portion is from 5 to 50 μm. An accuracy ofthe width and height of the core portion is not more than 5%, morepreferably not more than 1% of an average value.

FIG. 1 shows a diagrammatic cross-sectional view of a structure of atypical optical waveguide device. Numeral 1 represents a substrate,numeral 2 represents a core portion and numerals 4 and 5 represent cladportions. Such an optical waveguide device is used to connect opticalfunctional devices. Light coming out from a terminal of one opticalfunctional device is transmitted through the inside of the core portion2 of the optical waveguide device to a terminal of another opticalfunctional device while repeating total reflections, for example, on aninterface between the core portion 2 and the clad portions 4 and 5. Theoptical waveguide device can be optionally formed into a plane, strip,ridge or embedded type.

A material of the substrate of the optical waveguide device is notlimited particularly, and materials such as metal, semiconductormaterial, ceramic, glass, thermoplastic resin and thermo-setting resincan be used optionally.

FIG. 2 shows an example of production steps of an optical waveguidedevice using the material of the present invention. The opticalwaveguide device is produced using a photolithography technology. First,as shown in FIG. 2(a), a clad portion 4 is previously formed on asubstrate 1, and then a film 3 of the material of the present inventionwhich forms a core portion is formed. In forming the films of theoptical waveguide materials which form the clad portion 4 and the coreportion, it is preferable to coat the solutions of those materials by acoating means such as spin coating and cast coating, and the rotarycoating is particularly preferred. Each of the solutions of materials ispreferably prepared by dissolving in a solvent in a proper concentrationfor the thickness of each film and then filtrating, for example, througha filter having a pore size of about 0.2 μm.

The preferred concentration of each solution varies depending on acoating method. With respect to the resin for forming the core portion,the concentration is generally from 5 to 1,000 g, particularlypreferably from 30 to 500 g per liter of a solvent, and with respect tothe clad material, the concentration is generally from 1 to 1,000 g,particularly preferably from 30 to 500 g per liter of a solvent. Thepreferred concentration of a radiation-sensitive material is generallyfrom 100 to 500 g, particularly preferably from 300 to 400 g per literof a solvent.

As the solvent, there can be suitably used those mentioned above.

Then as shown in FIG. 2(b), the fluorine-containing prepolymer isirradiated with active energy ray 7 through a mask 6 having a specificpattern form. Then pre-baking is carried out as case demands. Byphoto-curing, the carbon-carbon double bonds in the fluorine-containingprepolymer (I) in the optical wavegiude material of the presentinvention are polymerized between the molecules thereof and thereby thecarbon-carbon double bonds in the polymer decrease or disappear. As aresult, hardness of the resin becomes high, a mechanical strength andheat resistance are increased and further the resin becomes insolublenot only in a solvent in which the resin is soluble before the curingbut also in many other kinds of solvents. Namely, the resin functions asa photoresist material. Then un-cured fluorine-containing prepolymer isdissolved and distilled off with a proper solvent to form the coreportion 2 having a specific pattern as shown in FIG. 2(c). Though theoptical waveguide device can be used as it is in the form having onlythe so-obtained core portion 2, it is preferable that after theformation of the core portion 2, the clad portion 5 is further formed asshown in FIG. 2(d). It is preferable that the clad portion 5 is formedby coating the solution of material by rotary coating, cast coating,roll coating or the like, and the rotary coating is particularlypreferred. It is also preferable that the solution of material for theclad portion 5 is prepared by dissolving a specific material in asolvent and then filtrating, for example, with a filter having a poresize of about 0.2 μm.

In case where the clad portion 5 is produced from the optical waveguidematerial of the present invention, examples of a solvent for preparingthe resin solution are, for instance, those exemplified in theabove-mentioned core portion 2 and clad portion 4.

In case of use of a core material which is not photo-cured, it has beenso far necessary to use a radiation-sensitive material. In that case,there is required a process for coating a radiation-sensitive materialon the core material, irradiating radiation through a pattern and thendry-developing by silylation treatment and/or Germylation and reactiveion etching treatment. This process is very complicated, which is afactor for an increase in cost.

The present invention is then explained by means of examples andpreparation examples, but is not limited to the examples.

In the following Examples and Preparation Examples, equipment andmeasuring conditions used for evaluation of physical properties are asfollows.

(1) NMR: NMR analyzer is AC-300 available from BRUKER CO., LTD.Measuring conditions of ¹H-NMR: 300 MHz (tetramethylsilane=0 ppm)Measuring conditions of ¹⁹F-NMR: 300 MHz (trichlorofluoromethane=0 ppm)

A ratio of conversion to CH₂═CF—C(═O)— (α-fluoroacryloyl) (5.2 to 5.8ppm (2H)) can be calculated from the data of ¹H-NMR analysis, and aratio of α-fluoroacryloyl group (−116 to −118 ppm (1F))/CF₂ and CF₃ in aside chain (−85 to −75 ppm (10F)) can be calculated from the data of¹⁹F-NMR analysis by usual method.

(2) IR analysis: Measuring is carried out at room temperature with aFourier-transform infrared spectrophotometer 1760× available from PerkinElmer Co., Ltd.

(3) GPC: A number average molecular weight is calculated from datameasured by gel permeation chromatography (GPC) by using GPC HLC-8020available from Toso Kabushiki Kaisha and columns available from ShodexCo., Ltd. (one GPC KF-801, one GPC KF-802 and two GPC KF-806M wereconnected in series) and flowing tetrahydrofuran (THF) as a solvent at aflowing rate of 1 ml/minute.

PREPARATION EXAMPLE 1 Synthesis of Homopolymer of Fluorine-ContainingAllyl Ether having OH Group

A 100 ml four-necked glass flask equipped with a stirrer and thermometerwas charged with 20.4 g ofperfluoro-(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol):

and 21.2 g of a perfluorohexane solution of 8.0% by weight of:[HCF₂CF₂₃COO₂and after the inside of the flask was sufficiently replaced withnitrogen gas, stirring was carried out at 20° C. for 24 hours innitrogen gas stream and a solid having a high viscosity was produced.

The obtained solid was dissolved in diethyl ether and then poured intoperfluorohexane, followed by separating and vacuum-drying to obtain 17.6g of a transparent colorless polymer.

According to ¹⁹F-NMR, ¹H-NMR and IR analyses, the polymer was afluorine-containing polymer consisting of the structural unit of theabove-mentioned fluorine-containing allyl ether and having hydroxyl atan end of its side chain. The number average molecular weight of thepolymer was 9,000 according to the GPC analysis using tetrahydrofuran(THF) as a solvent and the weight average molecular weight thereof was22,000.

Example 1 Synthesis of Curable Fluorine-Containing Prepolymer (I) havingα-Fluoroacryloyl Group

A 200 ml four-necked flask equipped with a reflux condenser,thermometer, stirrer and dropping funnel was charged with 80 ml ofdiethyl ether, 5.0 g of the fluorine-containing allyl ether homopolymerhaving hydroxyl which was obtained in Preparation Example 1 and 1.0 g ofpyridine, followed by cooling to 5° C. or lower with ice.

Then a solution obtained by dissolving 1.0 g of α-fluoroacrylic acidfluoride CH₂═CFCOF in 20 ml of diethyl ether was added thereto dropwiseover about 30 minutes while stirring in nitrogen gas stream.

After completion of the addition, the flask temperature was raised toroom temperature and the stirring was further continued for 4.0 hours.

The ether solution after the reaction was put in the dropping funnel,followed by washing with water, 2% hydrochloric acid solution, 5% NaClsolution and water and then drying with anhydrous magnesium sulfate.Then the ether solution was separated by filtration. Thus a curablefluorine-containing prepolymer was obtained.

According to ¹⁹F-NMR analysis, the curable fluorine-containingprepolymer was a copolymer comprising a fluorine-containing allyl etherhaving

group and a fluorine-containing allyl ether having OH group in a ratioof 40/60% by mole.

The prepolymer was coated on a NaCl plate and formed into a cast film atroom temperature. According to IR analysis of the cast film, anabsorption of a carbon-carbon double bond was observed at 1,661 cm⁻¹,and an absorption of C═O group was observed at 1,770 cm⁻¹.

Example 2 Synthesis of Curable Fluorine-Containing Prepolymer (I) havingα-Fluoroacryloyl Group

A curable fluorine-containing prepolymer (ether solution) wassynthesized in the same manner as in Example 1 except that 0.65 g ofα-fluoroacrylic acid fluoride (CH₂═CFCOF) and 1.0 g of pyridine wereused.

According to ¹⁹F-NMR analysis, the curable fluorine-containingprepolymer was a copolymer comprising a fluorine-containing allyl etherhaving

group and a fluorine-containing allyl ether having OH group in a ratioof 30/70% by mole.

According to IR analysis, an absorption of a carbon-carbon double bondand an absorption of C═O group were observed at the same positions,respectively as in Example 1.

Example 3 Synthesis of Curable Fluorine-Containing Prepolymer (I) havingα-Fluoroacryloyl Group

A curable fluorine-containing prepolymer (I) (ether solution) wassynthesized in the same manner as in Example 1 except that 0.35 g ofα-fluoroacrylic acid fluoride (CH₂═CFCOF) and 0.3 g of pyridine wereused.

According to ¹⁹F-NMR analysis, the curable fluorine-containingprepolymer was a copolymer comprising a fluorine-containing allyl etherhaving

group and a fluorine-containing allyl ether having OH group in a ratioof 15/85% by mole.

According to IR analysis, an absorption of a carbon-carbon double bondand an absorption of C═O group were observed at the same positions,respectively as in Example 1.

Example 4 Evaluation of Physical Properties of Photo-Cured Film which isOptical Waveguide Member

(1) Preparation of Optical Waveguide Material

The curable fluorine-containing prepolymer obtained in Example 1 wasdissolved in methyl ethyl ketone (MEK), and the concentration of thepolymer was adjusted to 50% by weight.

To 10 g of the obtained curable fluorine-containing prepolymer solutionwas added, as an active energy curing initiator (photoradicalgenerator), 1.7 g of a solution prepared by dissolving2-hydroxy-2-methylpropiophenone in MEK in a concentration of 1% byweight. Thus an optical waveguide material was produced.

(2) Production of Film of Optical Waveguide Material

The optical waveguide material (50% solution in MEK of thefluorine-containing prepolymer) obtained in (1) above was coated on apolyester film with an applicator so that a coating thickness after thedrying became a specific thickness (about 1 mm and about 100 μm). Aftervacuum-drying at 50° C. for ten minutes, the obtained cast film waspeeled from the polyester film to produce optical waveguide materials inthe form of un-cured films having a thickness of about 1 mm and about100 μm.

(3) Production of Cured Film by Irradiation of Light

After the drying, the film obtained in (2) above was irradiated withultraviolet light using a high pressure mercury lamp at room temperatureat an intensity of 3,000 mJ/cm²U to obtain a photo-cured film.

(4) Measurement of Physical Properties of Cured Film

The following physical properties of the obtained cured film wereevaluated.

(i) Measurement of Absorption Coefficient

A spectral transmittance curve of an about 1 mm thick sample (curedfilm) was obtained at a wavelength of from 300 to 1,700 nm using aself-recording spectrophotometer (U-3410 available from Hitachi, Ltd.).An absorption coefficient was calculated from the obtained spectrum bythe following equation.Absorption coefficient=Absorbance/Thickness of sample

The results are shown in Table 1.

(ii) Measurement of Refractive Index

A refractive index of an about 100 μm thick sample (a film before andafter curing) was measured using an Abbe's refractometer at 25° C. withlight having a wavelength of 550 nm. The results are shown in Table 1.

(iii) Thermal Characteristic (DSC)

Thermal characteristics were measured at a temperature raising rate of10° C./min using a differential calorimeter (DSC-50 available fromShimadzu Corporation), and it was found that any films had no clearcrystalline melting point peak and were non-crystalline.

(iv) Evaluation of Solvent Resistance

An about 1 mm thick cured film was dipped in acetone and the conditionthereof after a lapse of 24 hours at room temperature was observed withnaked eyes and evaluated by the following criteria. The results areshown in Table 1.

-   ∘: There is no change in appearance.-   X: Dissolved in acetone.    (v) Evaluation of Heat Resistance

An about 1 mm thick cured film was allowed to stand at 150° C. for eighthours and a change in its form was observed and evaluated with nakedeyes by the following criteria. The results are shown in Table 1.

-   ∘: There is no change in appearance.-   X: The film could not maintain its original form.

Examples 5 and 6

Production of films and evaluation of cured films were carried out inthe same manner as in Example 4 except that the fluorine-containingprepolymers shown in Table 1 (those produced in Examples 2 and 3,respectively) were used instead of the fluorine-containing prepolymerhaving α-fluoroacryloyl group which was obtained in Example 1. Theresults are shown in Table 1. Thermal characteristics thereof weredetermined using DSC and it was recognized that any of the films beforeand after the curing were non-crystalline.

Comparative Example 1

With respect to the un-cured film which was not subjected to irradiationof light, physical properties were evaluated in the same manner as inExample 4. The results are shown in Table 1.

TABLE 1 Ex. 4 Ex. 5 Ex. 6 Com. Ex. 1 Pre-polymer Ex. 1 Ex. 2 Ex. 3 Ex. 1Content of —O(C═O)CF═CH₂ group 40 30 15 40 Fluorine content (%) 57 58 5857 Active energy curing initiator 2-Hydroxy-2- 2-Hydroxy-2- 2-Hydroxy-2-2-Hydroxy-2- methyl- methyl- methyl- methyl- propiophenone propiophenonepropiophenone propiophenone Proportion to polymer (% by weight) 2.1 2.12.1 2.1 Amount of ultraviolet irradiation 3000 3000 3000 Not irradiated(mJ/cm²) Refractive index Before curing 1.362 1.359 1.356 1.362 Aftercuring 1.366 1.364 1.361 — Absorption coefficient (cm⁻¹) 1,310 nm 0.0400.043 0.047 0.040 1,550 nm 0.13 0.11 0.079 0.12 Solvent resistance ◯ ◯ ◯X Heat resistance ◯ ◯ ◯ X

Examples 7 to 10 Determination of Curing Reactivity by IR Analysis

(1) Preparation of Optical Waveguide Material (Fluorine-Containing ResinComposition for Coating)

Respective coating compositions (optical waveguide materials) wereprepared using the curable fluorine-containing prepolymer (I) obtainedin Example 1 by the same procedures as in Example 4 so that theconcentration of polymer and the amount of active energy curinginitiator became those shown in Table 2.

(2) Production of Film for IR Analysis

The above-mentioned coating compositions were coated on a polyester filmwith an applicator so that a coating thickness after drying became about100 μm, followed by drying at 50° C. for five minutes. Then the obtainedcoating films were peeled from the polyester film to obtain un-curedcast films.

(3) Measurement of Curing Reactivity by IR Analysis

According to IR analysis of the un-cured films, an absorption of acarbon-carbon double bond in the polymer was observed at 1,661 cm⁻¹.

(4) Measurement of Ratio of Curing Reaction

Attention was directed to the absorption of the carbon-carbon doublebond, and a change in intensity of the absorption after the lightirradiation was measured. A ratio of curing reaction was calculated bythe following equation.$( {1 - \frac{{{Peak}\quad{height}\quad{at}\quad 1,661\quad{cm}^{- 1}\quad{after}\quad{light}\quad{irradiation}}\quad}{{{Peak}\quad{height}\quad{at}\quad 1,661\quad{cm}^{- 1}\quad{before}\quad{light}\quad{irradiation}}\quad}} ) \times 100\quad\%$

The un-cured films obtained in (2) above were irradiated withultraviolet light at room temperature in irradiation amounts shown inTable 2 using a high pressure mercury lamp, and cured films wereobtained. The amount of irradiation was changed and the ratio of curingreaction represented by the above equation was calculated. The resultsare shown in Table 2.

TABLE 2 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Curable fluorine-containing polymer Ex.1 Ex. 2 Ex. 3 Ex. 1 Content of —O(C═O)CF═CH₂ group 40 40 40 40 (% bymole) Solvent MEK MEK MEK MEK Concentration of polymer 8 8 8 8 (% byweight) Active energy curing initiator 2-Hydroxy-2- 2-Hydroxy-2-2-Hydroxy-2- 2-Hydroxy-2- methyl- methyl- methyl- methyl- propiophenonepropiophenone propiophenone propiophenone Proportion to polymer (% byweight) 4.2 2.1 1.0 0.2 Ratio of curing reaction (%) Ultravioletirradiation amount   100 mJ/cm² 100 60 45 34 (disappeared)   500 mJ/cm²— 82 60 44 1,500 mJ/cm² — 100 74 55 (disappeared)

Example 11 Synthesis of Curable Fluorine-Containing Prepolymer (I)having α-fluoroacryloyl Group

A curable fluorine-containing prepolymer (I) (ether solution) wassynthesized in the same manner as in Example 1 except that 2.0 g ofα-fluoroacrylic acid fluoride (CH₂═CFCOF) and 2.0 g of pyridine wereused.

According to ¹⁹F-NMR analysis, this fluorine-containing prepolymer was acopolymer comprising a fluorine-containing allyl ether having

group and a fluorine-containing allyl ether having OH group in a ratioof 84:16% by mole.

According to IR analysis, an absorption of a carbon-carbon double bondand an absorption of C═O group were observed at the same positions as inExample 1, respectively.

Examples 12 to 14 Determination of Curing Reactivity by IR Analysis

(1) Preparation of Optical Waveguide Material (Fluorine-Containing ResinComposition for Coating)

Respective optical waveguide materials (coating compositions) wereprepared using the curable fluorine-containing prepolymer (I) obtainedin Example 11 by the same procedures as in Example 4 so that theconcentration of polymer and kind and amount of active energy curinginitiator became those shown in Table 3.

(2) Production of Film for IR Analysis

The films were produced in the same manner as in Example 7.

(3) Measurement of Ratio of Curing Reaction by IR Analysis

A ratio of curing reaction when light irradiation was carried out in anirradiation amount of 1,500 mJ/cm² was calculated in the same manner asin Example 7. The results are shown in Table 3.

Example 15

An optical waveguide material (fluorine-containing resin composition forcoating) containing a curing agent was prepared by adding, as a curingagent,

to the optical waveguide material (coating composition) obtained inExample 12 so that the amount thereof became 20% by weight based on thepolymer.

A film for IR analysis was produced using this resin composition in thesame manner as in Example 12, and a ratio of curing reaction wasdetermined. The results are shown in Table 3.

TABLE 3 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Curable fluorine-containing polymerEx. 11 Ex. 11 Ex. 11 Ex. 11 Content of —O(C═O)CF═CH₂ group 84 84 84 84(% by mole) Solvent MEK MEK MEK MEK Concentration of polymer 8 8 8 8 (%by weight) Active energy curing initiator 2-Hydroxy-2- 2,2-dimethoxy-Benzophenone 2-Hydroxy-2- methyl- 2-phenyl- methyl- propiophenoneacetophenone propiophenone Proportion to polymer (% by weight) 2.0 2.02.0 2.0 Curing agent — — — Polyfunctional acryl¹⁾ Proportion to polymer(% by weight) — — — 20 Ratio of curing reaction (%) 73.9 55.0 40.6 84.0(at 1,500 mJ/cm²) ¹⁾Polyfunctional acryl: CHhd2═CF(C═O)OCH₂—(CF₂)₆—CH₂O(C═O)CF═CH₂

Preparation Example 2 Synthesis of Fluorine-Containing Allyl EtherHomopolymer having OH Group

Synthesis of a polymer and refining of the obtained polymer were carriedout in the same manner as in Preparation Example 1 except that 20.0 g ofperfluoro-(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol)and 10.0 g of a perfluorohexane solution of 8.0% by weight of:[HCF₂CF₂COO₂were used. Thus 18.2 g of a transparent colorless polymer was obtained.

According to ¹⁹F-NMR, ¹H-NMR and IR analyses, the obtained polymer was afluorine-containing polymer consisting of the structural unit of theabove-mentioned fluorine-containing allyl ether and having hydroxyl atan end of its side chain. The number average molecular weight of thepolymer was 30,000 according to the GPC analysis using tetrahydrofuran(THF) as a solvent and the weight average molecular weight thereof was59,000.

Preparation Example 3 Synthesis of Copolymer ComprisingFluorine-Containing Allyl Ether having OH Group and Vinylidene Fluoride

A 300 ml stainless steel autoclave equipped with a valve, pressure gaugeand thermometer was charged with 34.2 g ofperfluoro-(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol),200 g of CH₃CCl₂F (HCFC-141b) and 0.16 g of methanol solution of 50% byweight of dinormalpropyl peroxy carbonate (NPP). While cooling with dryice/methanol solution, the inside of a system was sufficiently replacedwith nitrogen gas. Then 5.8 g of vinylidene fluoride (VdF) wasintroduced through the valve, followed by a reaction while shaking at40° C. With the advance of the reaction, 12 hours after starting of thereaction, a gauge pressure inside the system lowered from 4.4 MPaG (4.5kgf/cm²G) before the reaction to 0.98 MPaG (1.0 kgf/cm²G).

At that time, un-reacted monomer was released and a precipitated solidwas removed and dissolved in acetone, followed by re-precipitation witha solvent mixture of hexane and toluene (50/50) to separate a copolymer.The copolymer was vacuum-dried until a constant weight was reached.Thereby 31.2 g of a copolymer was obtained.

The components of the copolymer were VdF and the fluorine-containingallyl ether having OH group in a ratio of 55:45% by mole according to¹H-NMR and ¹⁹F-NMR analyses. The number average molecular weight of thecopolymer was 12,000 according to the GPC analysis using THF as asolvent and the weight average molecular weight thereof was 18,000.

Preparation Example 4 Synthesis of Fluorine-Containing Active EnergyCuring Initiator

A 200 ml four-necked flask equipped with a reflux condenser,thermometer, stirrer and dropping funnel was charged with 2.0 g of2-hydroxy-2-methylpropiophenone, 1.0 g of pyridine and 20 g of a mixture(HCFC-225) of CF₃CF₂CHCl/CClF₂CF₂CHClF and was cooled to 5° C. or lowerwith ice.

Thereto was added dropwise 2.5 g of:

over one hour with stirring in nitrogen gas stream. After completion ofthe addition, the stirring was further continued for 4.0 hours.

After the reaction, the ether solution was put in the dropping funneland washed with 2% hydrochloric acid solution and 5% NaCl solution,followed by separation of an organic layer, drying with anhydrousmagnesium sulfate and distillation to isolate 2.6 g of a product (yield:62%).

According to ¹H-NMR, ¹⁹F-NMR and IR analyses, the product was:

Example 16 Synthesis of Curable Fluorine-Containing Prepolymer (I)having αFluoroacryloyl Group

A 200 ml four-necked flask equipped with a reflux condenser,thermometer, stirrer and dropping funnel was charged with 40 ml ofmethyl ethyl ketone (MEK), 5.0 g of the fluorine-containing allyl etherhomopolymer having hydroxyl which was obtained in Preparation Example 2and 2.0 g of pyridine, and was cooled to 5° C. or lower with ice.

Thereto was added dropwise 1.2 g of α-fluoroacrylic acid fluoride overabout 30 minutes with stirring in nitrogen gas stream. After completionof the addition, the flask temperature was raised to room temperatureand the stirring was further continued for 4.0 hours.

After the reaction, the MEK solution was put in the dropping funnel andwashed with water, 2% hydrochloric acid solution, 5% NaCl solution andwater, followed by separation of an organic layer and drying withanhydrous magnesium sulfate to obtain a curable fluorine-containingprepolymer. A concentration of the polymer after filtrating was 10.7% byweight.

According to ¹⁹F-NMR analysis, the obtained fluorine-containingprepolymer was a copolymer comprising a fluorine-containing allyl etherhaving

group and a fluorine-containing allyl ether having OH group in a ratioof 30:70% by mole.

According to IR analysis which was carried out in the same manner as inExample 1, an absorption of a carbon-carbon double bond and anabsorption of C═O group were observed at 1,660 cm⁻¹ and 1,770 cm⁻¹,respectively.

Example 17 Synthesis of Curable Fluorine-Containing Prepolymer (I)having α-Fluoroacryloyl Group

A curable fluorine-containing prepolymer (I) (MEK solution) wassynthesized in the same manner as in Example 16 except that 5.0 g of thecopolymer comprising the fluorine-containing allyl ether having OH groupand VdF which was obtained in Preparation Example 3, 1.1 g of pyridineand 1.0 g of α-fluoroacrylic acid fluoride were used. A concentration ofthe polymer was 9.9% by weight.

According to ¹⁹F-NMR analysis, the obtained prepolymer was a copolymercomprising a fluorine-containing allyl ether having —

group and a fluorine-containing allyl ether having OH group in a ratioof 15:85% by mole.

Example 18 Evaluation of Physical Properties of Photo-Cured Film whichis an Optical Waveguide Member

(1) Preparation of Optical Waveguide Material

MEK was added to the fluorine-containing prepolymer (MEK solution)obtained in Example 16 to adjust the concentration of polymer to 50% byweight.

To the MEK solution of the fluorine-containing prepolymer was added2-hydroxy-2-methylpropiophenone as the active energy curing initiator sothat its amount became 2.0% by weight based on the polymer. However thesolution became turbid in white and there could not be obtainedcompatibility therebetween.

Therefore the fluorine-containing active energy curing initiatorobtained in Preparation Example 4 was added instead of2-hydroxy-2-methylpropiophenone so that its amount became 3.6% by weightbased on the polymer. As a result, a transparent colorless solution wasobtained and there was compatibility therebetween. The solution is theoptical waveguide material.

(2) Evaluation of Photo-Cured Film of Optical Waveguide Material

Evaluation was carried out in the same manner as in (2) to (4) ofExample 4 (an irradiation amount in (3) was 1,500 mJ/cm²) using theoptical waveguide material (coating composition) containing the curinginitiator which was prepared in (1) above, and a ratio of curingreaction when irradiating light at 1,500 mJ/cm² was measured in the samemanner as in Example 8. The results are shown in Table 4. It wasdetermined by DSC analysis that the material was non-crystalline.

Example 19 Evaluation of Physical Properties of Photo-Cured Film whichis an Optical Waveguide Member

(1) Preparation of Optical Waveguide Material

MEK was further added to the fluorine-containing prepolymer (MEKsolution) which was obtained in Example 17 to adjust the polymerconcentration to 8% by weight.

To this MEK solution of fluorine-containing prepolymer was added2-hydroxy-2-methylpropiophenone as the active energy curing initiator sothat its amount became 6.7% by weight based on the polymer. As a result,a transparent colorless solution was obtained and there wascompatibility therebetween. The solution is the optical waveguidematerial. It was determined by DSC analysis that the material wasnon-crystalline.

(2) Evaluation of Photo-Cured Film of Optical Waveguide Material

Evaluation was carried out in the same manner as in Example 18 using theobtained optical waveguide material (coating composition). The resultsare shown in Table 4.

TABLE 4 Ex. 18 Ex. 19 Pre-polymer Ex. 16 Ex. 17 Content of —O(C═O)CF═CH₂group 89 35 Fluorine content (%) 56 57 Active energy curing initiatorFluorine-containing 2-Hydroxy-2-methyl- initiator of Prep. Ex. 4propiophenone Proportion to polymer (% by weight) 3.6 6.7 Ultravioletirradiation amount (mJ/cm) 1500 1500 Ratio of curing reaction 88.7 75.7Refractive index Before curing 1.368 1.369 After curing 1.375 1.377Absorption coefficient (cm⁻¹) 1,310 nm 0.026 0.051 1,550 nm 0.22 0.28Solvent resistance ◯ ◯ Heat resistance ◯ ◯

Preparation Example 5 Synthesis of Copolymer of Fluorine-ContainingAllyl Ether having OH Group

A 100 ml four-necked glass flask equipped with a stirrer and thermometerwas charged with 5.2 g ofperfluoro-(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol):

(hereinafter referred to as “fluorine-containing allyl ether A”) and14.2 g of:

(hereinafter referred to as “fluorine-containing allyl ether B”),followed by sufficiently replacing the inside of the flask with nitrogengas and stirring at 20° C. for 24 hours in nitrogen gas stream. Therebya solid having a high viscosity was produced.

The obtained solid was dissolved in diethyl ether and then poured intoperfluorohexane, followed by separating and vacuum-drying to obtain 12.2g of a transparent colorless polymer.

According to ¹⁹F-NMR, ¹H-NMR and IR analyses, the polymer was afluorine-containing polymer comprising the structural units of theabove-mentioned two kinds of fluorine-containing allyl ethers and havinghydroxyl at an end of its side chain. The weight average molecularweight (Mw) of the polymer was 21,000 according to the GPC analysisusing tetrahydrofuran (THF) as a solvent and a ratio (Mw/Mn) thereof tothe number average molecular weight (Mn) was 1.3.

Also a 5% by weight decomposition temperature measured by the followingmethod was 360° C.

(Measurement of 5% by Weight Decomposition Temperature)

The polymer is heated at a temperature increasing rate of 10° C./minwith dry air of 200 ml/min using TG/DTA (TG/DTA220 available from SeikoDenshi Kabushiki Kaisha) and a temperature when 5% by weight of thermaldecomposition (weight reduction) arises is assumed to be the 5% byweight decomposition temperature.

Preparation Examples 6 to 9 Synthesis of Fluorine-Containing Allyl EtherHomopolymer and Copolymer Having OH Group

Polymerization was carried out in the same manner as in PreparationExample 5 except that the amounts of the two kinds offluorine-containing allyl ethers A and B were changed to those shown inTable 5. Thereby fluorine-containing copolymers comprising thestructural units of the above-mentioned two kinds of fluorine-containingallyl ethers and having hydroxyl at an end of a side chain thereof(Preparation Examples 6, 7 and 9) and a homopolymer of thefluorine-containing allyl ether A (Preparation Example 8) were obtained.Physical properties of those polymers are shown in Table 5.

TABLE 5 Preparation Example 5 6 7 8 9 Fluorine-containing allyl ether A(g) 5.2 10.3 15.3 30.2 72.1 B (g) 14.2 9.5 4.8 0 8.3 Amount of preparedpolymer (g) 12.2 13.1 13.1 19.6 50.2 Physical properties of polymer Mw(×10⁴) 2.1 2.2 2.7 3.0 1.9 Mw/Mn 1.3 1.5 1.5 1.7 1.5 5% Decomposition360 364 364 381 370 temperature (° C.)

Examples 20 to 24 Synthesis of Curable Fluorine-Containing Prepolymer(I) Having α-Fluoroacryloyl Group

Curable fluorine-containing prepolymers having α-fluoroacryloyl groupwere synthesized in the same manner as in Example 1 except that thefluorine-containing allyl ether polymers having OH group which wereprepared in Preparation Examples 5 to 9 were used instead of thefluorine-containing allyl ether polymer having OH group which wasprepared in Preparation Example 1 in amounts shown in Table 6 under thereaction conditions shown in Table 6.

According to ¹⁹F-NMR analysis of the obtained curablefluorine-containing prepolymer, contents (% by mole) of the structuralunits derived from the fluorine-containing allyl ethers A and B havingOH group were as shown in Table 6.

According to IR analysis of cast films which were obtained by coatingthe polymer on a NaCl plate and drying at room temperature, anabsorption of a carbon-carbon double bond and an absorption of C═O groupwere observed around 1,661 cm⁻¹ and around 1,770 cm⁻¹, respectively.

TABLE 6 Example 20 21 22 23 24 Polymer having OH group PreparationExample 5 6 7 8 9 Amount (g) 7.4 7.0 7.0 6.9 40.2 α-Fluoroacrylic acidfluoride (g) 1.0 1.8 2.6 3.1 18.3 MEK (g) 30 30 30 30 200 Pyridine (g)1.0 1.9 2.6 3.2 18.5 Reaction time 4.5 4.5 4.5 4.0 4.5 Fluorine content(% by weight) 62 59 57 55 56 Fluorine-containing allyl ether A 27 53 78100 88 (% by mole) Fluorine-containing allyl ether B 73 47 22 0 12 (% bymole)

Examples 25 to 29 Evaluation of Physical Properties of Photo-Cured Filmwhich is an Optical Waveguide Member)

Production of films and evaluation of cured films were carried out inthe same manner as in Example 4 except that the fluorine-containingprepolymers shown in Table 7 (those prepared in Examples 20 to 24,respectively) were used instead of the fluorine-containing prepolymerhaving α-fluoroacryloyl group which was prepared in Example 1. Theresults are shown in Table 7. It was determined according to DSCanalysis that the obtained prepolymers were non-crystalline.

TABLE 7 Ex. 25 Ex. 26 Ex. 27 Ex. 28 Ex. 29 Pre-polymer Ex. 20 Ex. 21 Ex.22 Ex. 23 Ex. 24 Content of —O(C═O)CF═CH₂ 27 53 78 100 88 group (% bymole) Fluorine content 62 59 57 55 56 (% by weight) Active energy curing2-Hydroxy-2- 2-Hydroxy-2- 2-Hydroxy-2- 2-Hydroxy-2- 2-Hydroxy-2-initiator methyl- methyl- methyl- methyl- methyl- propiophenonepropiophenone propiophenone propiophenone propiophenone Proportion topolymer 2.0 2.0 2.0 2.0 2.0 (% by weight) Ultraviolet irradiation 18001800 1800 1800 1800 amount (mJ/cm) Refractive index Before curing 1.3421.354 1.364 1.371 1.368 After curing 1.352 1.361 1.369 1.381 1.375Solvent resistance ◯ ◯ ◯ ◯ ◯ Heat resistance ◯ ◯ ◯ ◯ ◯

Example 30 Evaluation of Physical Properties of Photo-Cured Film whichis an Optical Waveguide Member)

(1) Preparation of Optical Waveguide Material

The curable fluorine-containing prepolymer obtained in Example 24 wasdissolved in propylene glycol monomethyl ether acetate (PGMEA) to obtaina solution having a prepolymer concentration of 40% by weight.

To 10 g of the PGMEA solution of fluorine-containing prepolymer wasadded 1.5 g of MEK solution of 1% by weight of the compound obtained inPreparation Example 4 as an active energy curing initiator (photoradicalinitiator) to prepare an optical waveguide material for coating.

(2) Production of Photo-Cured Film of Optical Waveguide Material

The optical waveguide material (coating composition) was spin-coated ona 5 inch silicon wafer to obtain an un-cured film having a thickness of10 μm. After drying, this film was irradiated with ultraviolet light atroom temperature at an intensity of 1,800 mJ/cm²U with a high pressuremercury lamp to produce a photo-cured film.

(3) Evaluation of Photo-Cured Film of Optical Waveguide Material

A refractive index in a near infrared region (1,300 nm and 1,550 nm) ofthe obtained cured film was measured with a Prism Coupler (Model 2010,trade name) available from Metricon Co., Ltd. The refractive indices at1,300 nm and 1,550 nm were 1.373 and 1.371, respectively.

Example 31 Evaluation of Physical Properties of Photo-Cured Film whichis an Optical Waveguide Member)

(1) Preparation of Optical Waveguide Material

The optical waveguide material for coating which was obtained in (1) ofExample 30 was used.

(2) Production of Photo-Cured Film of Optical Waveguide Material

A specific amount of the optical waveguide material (coatingcomposition) was poured into a concave of 15 mm×15 mm×1 mm and threekinds of un-cured cast films having different thicknesses were obtained.After drying, those films were irradiated with ultraviolet light at roomtemperature at an intensity of 1,800 mJ/cm²U with a high pressuremercury lamp to produce photo-cured films having different thicknesses(thickness: 280 μm, 450 μm and 1,020 μm).

(3) Evaluation of Photo-Cured Film of Optical Waveguide Material

An intensity of absorption of the photo-cured film was measured every 1nm in the wavelength range of from 900 to 1,700 nm using a highsensitivity spectrophotometer (MAC-1, trade name) available from JASCOCorporation (measuring temperature: 24° C.). An intensity of absorptionof the photo-cured films having different thicknesses was also measuredin the same manner as above. An effect of a surface reflection waseliminated by standardizing the intensity of absorption for eachthickness and an absorption loss of the material was evaluated. Theresults are shown in FIG. 3.

It can be seen from FIG. 3 that values of an absorption loss at 1,300 nmand 1,550 nm were 0.1 dB/cm and 0.5 dB/cm, respectively and veryexcellent transparency is exhibited in a near infrared region.

Example 32 Production of Optical Waveguide Device

An optical waveguide in an optical waveguide device was formed by thefollowing procedures.

The optical waveguide was produced using the optical waveguide materialprepared in Example 16 as a material for a core portion and thefluorine-containing prepolymer prepared in Example 1 as a material for aclad portion.

Those two materials were dissolved in methyl isobutyl ketone to make therespective solutions. First, the material for the clad portion wascoated on a plastic substrate or a silicon substrate in a thickness ofabout 15 μm. After baking and drying, on the film of the material forthe clad portion was coated the material for the core portion in athickness of about 8 μm. Then the film of the material for the coreportion was irradiated with light through a photomask for curing. Afterthat, un-cured part of the core film was flowed away with a solvent tomake a linear rectangular pattern of the core portion of 50 mm long×8 μmwide×8 μm high. Then as explained by means of FIG. 2, a clad portion wasformed on the core portion to make an optical waveguide.

Next, a transmission loss of the produced waveguide was measured bypassing light having a wavelength of 1,300 nm through the core portion.As a result, the transmission loss was 0.5 dB/cm.

Further the produced optical waveguide was allowed to stand at atemperature of 80° C. at a humidity of 85% RH for one week. Thetransmission loss did not change at all.

According to the present invention, there can be provided the opticalwaveguide material in which the polymer can have heat resistance andhigh elasticity by photo-curing while maintaining near infraredtransparency.

Further when the cured article obtained from the optical waveguidematerial is used as the optical waveguide member, there can be providedthe optical waveguide device having heat resistance, small waterabsorption and improved near infrared transparency.

1. An optical waveguide comprising a core portion and a clad portion,wherein at least one of the core portion and clad portion is obtainedfrom a cured article produced by curing a curable fluorine-containingprepolymer (I) which: (1) is a non-crystalline polymer having a fluorinecontent of not less than 25% by weight, (2) has a carbon-carbon doublebond in the polymer side chain and/or at an end of the polymer trunkchain, and (3) has a number average molecular weight of 5000 to 100000.2. The optical waveguide of claim 1, wherein the fluorine-containingprepolymer (I) is a polymer having a maximum absorption coefficient ofnot more than 1 cm⁻¹ in a wavelength range of from 1,290 to 1,320 nm. 3.The optical waveguide of claim 1, wherein the fluorine-containingprepolymer (I) is a polymer having a maximum absorption coefficient ofnot more than 1 cm⁻¹ in a wavelength range of from 1,530 to 1,570 nm. 4.The optical waveguide of claim 1, wherein the fluorine-containingprepolymer (I) has a carbon-carbon double bond at an end of its sidechain.
 5. The optical waveguide of claim 1, wherein thefluorine-containing prepolymer (I) is a fluorine-containing polymerhaving a number average molecular weight of from 5000 to 100000 andrepresented by the formula (1):MA  (1) in which the structural unit M is a structural unit derivedfrom a fluorine-containing ethylenic monomer and represented by theformula (M):

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; X⁴ and X⁵ are the same or different and each is H, F orCF₃; Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to3; b and c are the same or different and each is 0 or 1, the structuralunit A is a structural unit derived from monomer copolymerizable withthe fluorine-containing ethylenic monomer providing the structural unitM, and the structural unit M and the structural unit A are contained inamounts of from 0.1 to 100% by mole and from 0 to 99.9% by mole,respectively.
 6. The optical waveguide of claim 5, wherein thefluorine-containing prepolymer (I) is the fluorine-containing polymer ofthe formula (1) and the structural unit M is a structural unit M1derived from a fluorine-containing ethylenic monomer and represented bythe formula (M1):

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; X⁴ and X⁵ are the same or different and each is H, F orCF₃; Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to3; c is 0 or
 1. 7. The optical waveguide of claim 5, wherein thefluorine-containing prepolymer (I) is the fluorine-containing polymer ofthe formula (1) and the structural unit M is a structural unit M2derived from a fluorine-containing ethylenic monomer and represented bythe formula (M2):

wherein Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond.
 8. The optical waveguide of claim5, wherein the fluorine-containing prepolymer (I) is thefluorine-containing polymer of the formula (1) and the structural unit Mis a structural unit M3 derived from a fluorine-containing ethylenicmonomer and represented by the formula (M3):

wherein Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond.
 9. The optical waveguide of claim5, wherein at least one of Y¹ of Rf in said formula (M) is bonded to anend of Rf.
 10. The optical waveguide of claim 9, wherein Y¹ of Rf insaid formula (M) is:O_(d)C═O_(c)Y² wherein —Y² is an alkenyl group orfluorine-containing alkenyl group having 2 to 5 carbon atoms and anethylenic carbon-carbon double bond at its end; d and e are the same ordifferent and each is 0 or
 1. 11. The optical waveguide of claim 9,wherein Y¹ of Rf in said formula M)is:—O(C═O)CX⁶═CX⁷X⁸ wherein X⁶ is H, F, CH₃ or CF₃; X⁷ and X⁸ are the sameor different and each is H or F.
 12. The optical waveguide of claim 1,wherein a maximum absorption coefficient of the cured article is notmore than 1 cm⁻¹ in a wavelength range of from 1,290 to 1,320 nm. 13.The optical waveguide of claim 1, wherein a maximum absorptioncoefficient of the cured article is not more than 1 cm⁻¹ in a wavelengthrange of from 1,530 to 1,570 nm.
 14. An optical waveguide typefunctional device comprising a core portion and a clad portion, whereinat least one of the core portion and clad portion is obtained from acured article produced by curing a curable fluorine-containingprepolymer (I) which: (1) is a non-crystalline polymer having a fluorinecontent of not less than 25% by weight, (2) has a carbon-carbon doublebond in the polymer side chain and/or at an end of the polymer trunkchain, and (3) has a number average molecular weight of 5000 to 100000.15. The optical waveguide type functional device of claim 14, whereinthe fluorine-containing prepolymer (I) is a polymer having a maximumabsorption coefficient of not more than 1 cm⁻¹ in a wavelength range offrom 1,290 to 1,320 nm.
 16. The optical waveguide type functional deviceof claim 14, wherein the fluorine-containing prepolymer (I) is a polymerhaving a maximum absorption coefficient of not more than 1 cm⁻¹ in awavelength range of from 1,530 to 1,570 nm.
 17. The optical waveguidetype functional device of claim 14, wherein the fluorine-containingprepolymer (I) has a carbon-carbon double bond at an end of its sidechain.
 18. The optical waveguide type functional device of claim 14,wherein the fluorine-containing prepolymer (I) is a fluorine-containingpolymer having a number average molecular weight of from 5000 to 100000and represented by the formula (1):MA  (1) in which the structural unit M is a structural unit derivedfrom a fluorine-containing ethylenic monomer and represented by theformula (M):

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; X⁴ and X⁵ are the same or different and each is H, F orCF₃; Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to3; b and c are the same or different and each is 0 or 1, the structuralunit A is a structural unit derived from monomer copolymerizable withthe fluorine-containing ethylenic monomer providing the structural unitM, and the structural unit M and the structural unit A are contained inamounts of from 0.1 to 100% by mole and from 0 to 99.9% by mole,respectively.
 19. The optical waveguide type functional device of claim18, wherein the fluorine-containing prepolymer (I) is thefluorine-containing polymer of the formula (1) and the structural unit Mis a structural unit M1 derived from a fluorine-containing ethylenicmonomer and represented by the formula (M1):

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; X⁴ and X⁵ are the same or different and each is H, F orCF₃; Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to3; c is 0 or
 1. 20. The optical waveguide type functional device ofclaim 18, wherein the fluorine-containing prepolymer (I) is thefluorine-containing polymer of the formula (1) and the structural unit Mis a structural unit M2 derived from a fluorine-containing ethylenicmonomer and represented by the formula (M2):

wherein Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond.
 21. The optical waveguide typefunctional device of claim 18, wherein the fluorine-containingprepolymer (I) is the fluorine-containing polymer of the formula (1) andthe structural unit M is a structural unit M3 derived from afluorine-containing ethylenic monomer and represented by the formula(M3):

wherein Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond.
 22. The optical waveguide typefunctional device of claim 18, wherein at least one of Y¹ of Rf in saidformula (M) is bonded to an end of Rf.
 23. The optical waveguide typefunctional device of claim 22, wherein Y¹ of Rf in said formula (M) is:O_(d)C═OY² wherein Y² is an alkenyl group or fluorine-containingalkenyl group having 2 to 5 carbon atoms and an ethylenic carbon-carbondouble bond at its end; d and e are the same or different and each is 0or
 1. 24. The optical waveguide type functional device of claim 22,wherein Y¹ of Rf in said formula (M) is:  —O(C═O)CX⁶═CX⁷X⁸ wherein X⁶ isH, F, CH₃ or CF₃; X⁷ and X⁸ are the same or different and each is H orF.
 25. The optical waveguide type functional device of claim 14, whereina maximum absorption coefficient of the cured article is not more than 1cm⁻¹ in a wavelength range of from 1,290 to 1,320 nm.
 26. The opticalwaveguide type functional device of claim 14, wherein a maximumabsorption coefficient of the cured article is not more than 1 cm⁻¹ in awavelength range of from 1,530 to 1,570 nm.
 27. An optical waveguidedevice produced by connecting optical functional devices with theoptical waveguide of claim
 1. 28. A method of producing an opticalwaveguide device comprising the following steps (A) to (C): (A) a stepfor forming a clad portion on a substrate, (B) a step for forming, onsaid clad portion, a film of fluorine-containing waveguide materialcomprising a curable fluorine-containing prepolymer (1) which: (1) is anon-crystalline polymer having a fluorine content of not less than 25%by weight, (2) has a carbon-carbon double bond in the polymer side chainand/or at an end of the polymer trunk chain, and (3) has a numberaverage molecular weight of 5000 to 100000 and an active energy curinginitiator (II), and (C) a step for forming a core portion comprising acured article of the fluorine-containing prepolymer (I) by irradiatingthe film of fluorine-containing waveguide material with active energyray.